JP2011095666A - Electrophotographic photoreceptor, process cartridge and electrophotographic apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor in which fluctuation in the sensitivity by an environment is suppressed and fluctuation in the potential by duration is moderate. <P>SOLUTION: The electrophotographic photoreceptor includes a conductive support, an intermediate layer provided on the conductive support, and a photosensitive layer provided on the intermediate layer, wherein the intermediate layer contains a polyolefin resin containing repeating structural units (A2) and others, and the mass ratio (%) of (A2) in the polyolefin resin is set to 0.01 mass% or more and 30 mass% or less. The repeating structural units (A2) are expressed by formula (21) and formula (22). In formula (21) and formula (22), R<SP>21</SP>to R<SP>24</SP>each independently represent a hydrogen atom, an alkyl group, a phenyl group or a monovalent group expressed by -Y<SP>21</SP>COOH (where Y<SP>21</SP>represents a single bond, an alkylene group or an arylene group); R<SP>25</SP>and R<SP>26</SP>each independently represent a hydrogen atom, an alkyl group or a phenyl group; and X<SP>21</SP>represents a divalent group expressed by -Y<SP>22</SP>COOCOY<SP>23</SP>- (where Y<SP>22</SP>and Y<SP>23</SP>each independently represent a single bond, an alkylene group or an arylene group), provided that at least one of R<SP>21</SP>to R<SP>24</SP>represents a monovalent group expressed by -Y<SP>21</SP>COOH. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an electrophotographic photosensitive member, and also relates to a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.

  The electrophotographic photoreceptor basically comprises a photosensitive layer for forming an electrostatic latent image by charging and exposure, and a conductive support for providing the photosensitive layer. Currently, semiconductor lasers are the main light source used in electrophotographic apparatuses, and charge generating materials used for the charge generation layer of electrophotographic photosensitive members are also sensitive to relatively long wavelengths of around 790 nm of the oscillation wavelength of the semiconductor laser. Materials with are being considered. Among these, various organic phthalocyanines such as aluminum chlorophthalocyanine, chloroindium phthalocyanine, oxyvanadyl phthalocyanine, chlorogallium phthalocyanine, magnesium phthalocyanine and oxytitanium phthalocyanine having sensitivity to long wavelength light, or organic pigments such as metal-free phthalocyanine. Is often used.

  In order to improve characteristics such as developability, an intermediate layer is provided between the conductive support and the photosensitive layer. Materials for forming the intermediate layer include polyamide (Patent Document 1), polyester (Patent Document 2), vinyl acetate-ethylene copolymer (Patent Document 3), chlorinated ethylene (Patent Document 4), maleic anhydride A coalescence (patent document 5), polyvinyl butyral (patent document 6) and a quaternary ammonium salt-containing polymer (patent document 7) are known. And the intermediate | middle layer is formed by apply | coating the coating liquid for intermediate | middle layers obtained by dissolving these resin in a solvent, and heating this.

  However, in many cases, these resins have high polar functional groups in their molecular chains and thus have high hygroscopicity, and the resistance value varies greatly depending on the humidity of the outside world. Therefore, when the intermediate layer is formed of these resins alone, the residual potential increases, the electrical characteristics of the electrophotographic photosensitive member fluctuate in an environment of low temperature and low humidity, and high temperature and high humidity, and image defects are not improved sufficiently. .

JP 58-95351 A JP-A-52-20836 JP-A-48-261141 JP 2005-10591 A JP 52-10138 A JP-A-57-90639 JP 51-126149 A

  An object of the present invention is to provide an electrophotographic photosensitive member in which fluctuations in environmental sensitivity are suppressed and fluctuations in endurance potential are good (potential fluctuations when repeatedly used), and a process cartridge having the electrophotographic photosensitive member and It is to provide an electrophotographic apparatus.

  As a result of intensive studies on the above problems, the present inventors have completed the present invention shown below.

（式（１１）中、Ｒ^１１〜Ｒ^１４は、それぞれ独立に、水素原子、アルキル基を示す。）（Ａ２）：下記式（２１）または（２２）で示される繰り返し構造単位

（式（２１）および（２２）中、Ｒ^２１〜Ｒ^２４は、それぞれ独立に、水素原子、アルキル基、フェニル基または−Ｙ^２１ＣＯＯＨ（Ｙ^２１は、単結合、アルキレン基またはアリーレン基を示す。）で示される１価の基を示し、Ｒ^２５およびＲ^２６は、それぞれ独立に、水素原子、アルキル基またはフェニル基を示し、Ｘ^２１は、−Ｙ^２２ＣＯＯＣＯＹ^２３−（Ｙ^２２およびＹ^２３は、それぞれ独立に、単結合、アルキレン基またはアリーレン基を示す。）で示される２価の基を示す。ただし、Ｒ^２１〜Ｒ^２４のうち少なくとも１つは−Ｙ^２１ＣＯＯＨで示される１価の基である。）
（Ａ３）：下記式（３１）、（３２）、（３３）または（３４）で示される繰り返し構造単位

（式（３１）〜（３４）中、Ｒ^３１〜Ｒ^３５は、それぞれ独立に、水素原子またはメチル基を示し、Ｒ^４１〜Ｒ^４３は、それぞれ独立に、炭素数１〜１０のアルキル基を示し、Ｒ^５１〜Ｒ^５３は、それぞれ独立に、水素原子または炭素数１〜１０のアルキル基を示す。）
また、本発明は、上記電子写真感光体を有するプロセスカートリッジおよび電子写真装置である。 The present invention relates to an electrophotographic photosensitive member having a conductive support, an intermediate layer provided on the conductive support, and a photosensitive layer provided on the intermediate layer.
The intermediate layer contains a polyolefin resin having the following (A1), (A2) and (A3), and the mass ratio (%) of (A2) in the polyolefin resin is 0.01% by mass or more and 30% by mass or less. An electrophotographic photosensitive member characterized by the above.
(A1): Repeating structural unit represented by the following formula (11)

(In formula (11), R ^{11 to} R ¹⁴ each independently represents a hydrogen atom or an alkyl group.) (A2): Repeating structural unit represented by the following formula (21) or (22)

(In the formulas (21) and (22), R ^{21 to} R ²⁴ each independently represents a hydrogen atom, an alkyl group, a phenyl group or —Y ²¹ COOH (Y ²¹ represents a single bond, an alkylene group or an arylene group). .), R ²⁵ and R ²⁶ each independently represent a hydrogen atom, an alkyl group or a phenyl group, and X ²¹ represents —Y ²² COOCOY ²³ — (Y ²² and Y ^23. Each independently represents a single bond, an alkylene group or an arylene group.), Wherein at least one of R ^{21 to} R ²⁴ is a monovalent group represented by —Y ²¹ COOH. The base of
(A3): repeating structural unit represented by the following formula (31), (32), (33) or (34)

(In formulas (31) to (34), R ^{31 to} R ³⁵ each independently represent a hydrogen atom or a methyl group, and R ^{41 to} R ⁴³ each independently represents an alkyl group having 1 to 10 carbon atoms. R ^{51 to} R ⁵³ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)
The present invention also provides a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.

  According to the present invention, it is possible to provide an electrophotographic photosensitive member in which the environmental fluctuation of sensitivity is suppressed and the durability potential fluctuation is good, and a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.

1 is a diagram illustrating an example of a schematic configuration of an electrophotographic apparatus including a process cartridge having the electrophotographic photosensitive member of the present invention.

（式（１１）中、Ｒ^１１〜Ｒ^１４は、それぞれ独立に、水素原子、アルキル基を示す。）（Ａ２）：下記式（２１）または（２２）で示される繰り返し構造単位

（式（２１）および（２２）中、Ｒ^２１〜Ｒ^２４は、それぞれ独立に、水素原子、アルキル基、フェニル基または−Ｙ^２１ＣＯＯＨ（Ｙ^２１は、単結合、アルキレン基またはアリーレン基を示す。）で示される１価の基を示し、Ｒ^２５およびＲ^２６は、それぞれ独立に、水素原子、アルキル基またはフェニル基を示し、Ｘ^２１は、−Ｙ^２２ＣＯＯＣＯＹ^２３−（Ｙ^２２およびＹ^２３は、それぞれ独立に、単結合、アルキレン基またはアリーレン基を示す。）で示される２価の基を示す。ただし、Ｒ^２１〜Ｒ^２４のうち少なくとも１つは−Ｙ^２１ＣＯＯＨで示される１価の基である。）
（Ａ３）：下記式（３１）、（３２）、（３３）または（３４）で示される繰り返し構造単位

（式（３１）〜（３４）中、Ｒ^３１〜Ｒ^３５は、それぞれ独立に、水素原子またはメチル基を示し、Ｒ^４１〜Ｒ^４３は、それぞれ独立に、炭素数１〜１０のアルキル基を示し、Ｒ^５１〜Ｒ^５３は、それぞれ独立に、水素原子または炭素数１〜１０のアルキル基を示す。） Hereinafter, the electrophotographic photoreceptor of the present invention will be described in detail.
The electrophotographic photosensitive member of the present invention is an electrophotographic photosensitive member having a conductive support, an intermediate layer provided on the conductive support, and a photosensitive layer provided on the intermediate layer. A polyolefin resin having the following (A1), (A2) and (A3) is contained, and the mass ratio (%) of (A2) in the polyolefin resin is 0.01% by mass or more and 30% by mass or less. And
(A1): Repeating structural unit represented by the following formula (11)

(In formula (11), R ^{11 to} R ¹⁴ each independently represents a hydrogen atom or an alkyl group.) (A2): Repeating structural unit represented by the following formula (21) or (22)

(In the formulas (21) and (22), R ^{21 to} R ²⁴ each independently represents a hydrogen atom, an alkyl group, a phenyl group or —Y ²¹ COOH (Y ²¹ represents a single bond, an alkylene group or an arylene group). .), R ²⁵ and R ²⁶ each independently represent a hydrogen atom, an alkyl group or a phenyl group, and X ²¹ represents —Y ²² COOCOY ²³ — (Y ²² and Y ^23. Each independently represents a single bond, an alkylene group or an arylene group.), Wherein at least one of R ^{21 to} R ²⁴ is a monovalent group represented by —Y ²¹ COOH. The base of
(A3): repeating structural unit represented by the following formula (31), (32), (33) or (34)

(In formulas (31) to (34), R ^{31 to} R ³⁵ each independently represent a hydrogen atom or a methyl group, and R ^{41 to} R ⁴³ each independently represents an alkyl group having 1 to 10 carbon atoms. R ^{51 to} R ⁵³ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)

That is, the intermediate layer of the electrophotographic photosensitive member of the present invention contains a polyolefin resin having the above (A1), (A2) and (A3), and the mass ratio (%) of (A2) in the polyolefin resin is 0. 0.01 mass% or more and 30 mass% or less. When the mass ratio (%) of (A2) is less than 0.01 mass%, the durability fluctuation tends to increase, and when the mass ratio (%) exceeds 30 mass%, the sensitivity deteriorates and the environment varies. Becomes larger.
In addition, the intermediate layer used in the present invention may contain metal oxide particles, an organic electron transport material, and carbon black as necessary, and the mass ratio (%) of the polyolefin resin in the intermediate layer is 25 mass. It is preferable that it is% -100 mass%.

The mass ratio (%) of (A1) and (A3) in the polyolefin resin is
Formula (II): 55/45 ≦ (A1) / (A3) ≦ 99/1
It is preferable from the viewpoint of further improving the effects of the present invention. The mass ratio (%) of (A1) alone in the polyolefin resin is preferably 60% by mass or more, and more preferably 70% by mass or more. When the mass ratio (%) of (A1) is in such a range, the influence due to environmental fluctuations is reduced.

In order to improve the effect of the present invention, the mass ratio (%) of (A2) in the polyolefin resin is preferably 0.01% by mass or more and 10% by mass or less, and preferably 0.01% by mass or more and 5% by mass or less. More preferably, it is more preferably 3% by mass or more and 5% by mass or less.
The mass ratio (%) of (A1), (A2) and (A3) in the polyolefin resin preferably satisfies the following formula (I), and more preferably satisfies the following formula (III).
Formula (I): 0.01 ≦ (A2) / {(A1) + (A2) + (A3)} × 100 ≦ 10
Formula (III): 0.01 ≦ (A2) / {(A1) + (A2) + (A3)} × 100 ≦ 5

  The polyolefin resin used in the present invention is a copolymer, and is a resin synthesized by using monomers having a carbon-carbon double bond as raw materials and copolymerizing them.

The monomer for constituting (A2) in the present invention is a compound having at least one or both of a carboxylic acid group and a carboxylic anhydride group in the compound molecule (in the monomer unit). The compound having at least one of the carboxylic acid group and the carboxylic acid anhydride group is preferably an unsaturated carboxylic acid and / or an anhydride thereof. Specific examples include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid and crotonic acid, as well as unsaturated dicarboxylic acid half esters and half amides. Among these, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferable, and acrylic acid and maleic anhydride are particularly preferable.
Moreover, the form of the said copolymer is not specifically limited, A random copolymer, a block copolymer, and a graft copolymer are mentioned.

In the above formula (21), R ^{21 to} R ²⁴ are each independently a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, a phenyl group or —Y ²¹ COOH (Y ²¹ is a single bond, having 1 to 4 carbon atoms). A monovalent group represented by the formula (1), and at least one of R ^{21 to} R ²⁴ is preferably a monovalent group represented by —Y ²¹ COOH. . Three of R ^{21 to} R ²⁴ are hydrogen atoms, one is —COOH, or two of R ^{21 to} R ²⁴ are hydrogen atoms, one is a methyl group, and one is —COOH. More preferred.
In Formula (22), R ²⁵ and R ²⁶ are each independently preferably a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, or a phenyl group, and X ²¹ represents —Y ²² COOCOY ²³ — ( Y ²² and Y ²³ each independently preferably represent a single bond, a C 1-4 alkylene group or an arylene group. R ²⁵ and R ²⁶ are more preferably a hydrogen atom, and X ²¹ is more preferably —COOCO—.

In addition, unsaturated carboxylic acid anhydrides such as maleic anhydride form an acid anhydride structure in which adjacent carboxyl groups are dehydrated in the dry state of the resin. However, for example, in an aqueous medium containing a basic compound, part or all of the ring-opened carboxylic acid,
Or it becomes easy to take the structure of the salt. In the present invention, when the amount of the compound having a carboxylic acid group or a carboxylic acid anhydride group is defined based on the amount of the carboxyl group of the resin, all the carboxylic acid anhydride groups in the resin are ring-opened. It is calculated assuming that it is based.

The following compounds can be illustrated as a monomer for constituting (A3) in the present invention.
Formula (31): (Meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate.
Formula (32): Maleates such as dimethyl maleate, diethyl maleate, and dibutyl maleate.
Formula (33): (Meth) acrylic acid amides.
Formula (34): Vinyl alcohol obtained by saponifying alkyl vinyl ethers and vinyl esters such as methyl vinyl ether and ethyl vinyl ether with a basic compound.
In addition, these compounds can also be used individually or as a mixture.

Among these, (meth) acrylic acid esters are preferable, and methyl acrylate or ethyl acrylate is more preferable. That is, in the above formula (31), R ³¹ is more preferably a hydrogen atom, and R ⁴¹ is more preferably methyl or ethyl. Further, as described above, the mass ratio (%) of (A3) in the polyolefin resin is
Formula (II): 55/45 ≦ (A1) / (A3) ≦ 99/1
It is preferable that it is the quantity which satisfy | fills. (A3) The single mass ratio (%) is preferably 1% by mass or more and 20% by mass or less, and more preferably 10% by mass or more and less than 20% by mass. When the mass ratio (%) of (A3) in the polyolefin resin satisfies the above range, the influence due to durability fluctuation tends to be small.

Examples of the monomer for constituting (A1) in the present invention include alkenes such as ethylene, propylene, isobutylene, 1-butene, 1-pentene and 1-hexene. These can be used alone or as a mixture. Among these, alkenes having 2 to 4 carbon atoms such as ethylene, propylene, isobutylene and 1-butene are more preferable, and ethylene is particularly preferable. That is, in the above formula (11), R ^{11 to} R ¹⁴ are each independently preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ^{11 to} R ¹⁴ are all preferably hydrogen. preferable.

  The polyolefin resin used in the present invention is particularly preferably a terpolymer comprising ethylene, methyl (meth) acrylate or ethyl (meth) acrylate, and maleic anhydride. Specific examples of the terpolymer include ethylene-maleic anhydride-acrylic acid ester terpolymer or ethylene-maleic anhydride-methacrylic acid ester terpolymer.

  In the polyolefin resin used in the present invention, other monomer-derived components (repeating structural units) other than those described above may be contained as constituent components of the copolymer to the extent that the effects of the present invention are not impaired. Specific examples of other monomers include, for example, dienes, (meth) acrylonitrile, halogenated vinyls, halogenated vinylidenes, carbon monoxide, and carbon disulfide. In addition, it is preferable that the mass ratio (%) of the total amount of (A1), (A2), and (A3) in the polyolefin resin is 90% by mass to 100% by mass.

The molecular weight of the polyolefin resin used in the present invention is not particularly limited, but those having a molecular weight of 10,000 to 100,000 are preferably used, and more preferably 20,000 to 50,000. Further, the synthesis method is not particularly limited. The polyolefin resin can be obtained by, for example, high-pressure radical copolymerization of a monomer for constituting the polyolefin resin in the presence of a radical generator. As specific methods for synthesizing polyolefin resins, Chapters 1 to 4 (Kyoritsu Shuppan Co., Ltd.) of “New Polymer Experimental 2 Polymer Synthesis and Reaction (1)”, Japanese Patent Application Laid-Open No. 2003-105145. It is possible to use a known method described in Japanese Patent Laid-Open No. 2003-147028.

In the present invention, the properties of the resin were measured or evaluated by the following methods.
(1) Content of unsaturated carboxylic acid component in polyolefin resin shown in (A2) The acid value of the polyolefin resin was measured according to JIS K5407, and the content (graft ratio) of unsaturated carboxylic acid was determined from the value. Obtained from the following equation.
Content of unsaturated carboxylic acid component (mass%) = (mass of grafted unsaturated carboxylic acid) / (mass of raw material polyolefin resin) × 100
(2) Composition of resin other than (A2) Obtained by performing ¹ H-NMR and ¹³ C-NMR analysis (manufactured by Varian Technologies Japan Limited, 300 MHz) at 120 ° C. in orthodichlorobenzene (d4). It was. ^{In 13} C-NMR analysis, measurement was performed using a gated decoupling method in consideration of quantitativeness.

The intermediate layer coating solution can be prepared by dissolving a polyolefin resin in a solvent, by preparing a molten state by maintaining the polyolefin resin at a temperature higher than the softening point of the polyolefin resin, There is a method of preparing by preparing a dispersion by heating and stirring.
Further, the intermediate layer is formed by applying the intermediate layer coating solution by a coating method such as a dip coating method (dip coating method), a roll coating method, a spray coating method, a curtain coating method, or a spin coating method. However, the dip coating method is preferable from the viewpoint of efficiency / productivity.

  As the conductive support used in the present invention, for example, a metal or alloy such as aluminum, nickel, copper, gold, iron, polyester, polycarbonate, polyimide, an insulating support such as glass, aluminum, silver, Conductive support formed by forming a thin film of a metal such as gold or a conductive material such as indium oxide or tin oxide, and conductivity obtained by dispersing carbon and conductive filler in resin A support can be illustrated. The shape of the conductive support is not particularly limited, and a plate, drum, or belt shape is used as necessary. The surface of these conductive supports is an electrochemical treatment such as anodic oxidation for improving electrical characteristics or adhesion, and acidity mainly composed of alkali phosphate, phosphoric acid or tannic acid. Chemical treatment using a solution obtained by dissolving a metal salt compound or a metal salt of a fluorine compound in an aqueous solution may be performed.

In addition, when an electrophotographic photosensitive member is used in an electrophotographic apparatus using a single wavelength laser beam, the surface of the conductive support is preferably moderately roughened in order to suppress interference fringes.
The surface of the conductive support is preferably treated by honing, blasting, cutting, or electrolytic polishing. Alternatively, a conductive layer made of a conductive metal oxide and a binder resin is preferably formed on a conductive support of aluminum or an aluminum alloy.

As the honing treatment, there are dry and wet treatment methods, and any of them may be used. The wet honing treatment is a method in which a powdery abrasive is suspended in a liquid such as water and sprayed onto the surface of the support at a high speed to roughen the surface. The surface roughness is determined by spraying pressure, speed, and abrasive. The amount, type, shape, size, hardness, specific gravity, and suspension temperature can be controlled. On the other hand, the dry honing treatment is a method in which an abrasive is blown onto the surface of the support with air at a high speed to roughen the surface, and the surface roughness can be controlled by the same method as the wet honing treatment. Examples of the abrasive used for the wet or dry honing treatment include particles such as silicon carbide, alumina, iron, and glass beads.

  In the case where the conductive layer is formed by applying the conductive layer made of the conductive metal oxide and the binder resin on the conductive support of aluminum or aluminum alloy, the conductive layer contains conductive particles. Is preferred. In this method, by containing conductive particles in the conductive layer, the laser beam is diffusely reflected to suppress interference fringes, and there is also an effect of concealing scratches and protrusions on the surface of the conductive support. For example, zinc oxide, titanium oxide, or barium sulfate is used as the conductive particles. Moreover, it is also possible to set it as a specific resistance suitable as a filler by providing a conductive coating layer with tin oxide on the conductive particles as necessary.

The specific resistance of the conductive particles is preferably 0.1 to 1,000 Ω · cm, more preferably 1 to 1,000 Ω · cm. In the present invention, the specific resistance of the conductive particles was measured using a resistance measuring apparatus Loresta AP (Loresta Ap) manufactured by Mitsubishi Chemical Corporation. The conductive particles to be measured were hardened at a pressure of 500 kg / cm ² and attached to the measuring device as a coin-like sample.

  Moreover, it is preferable that the average particle diameter of the said electroconductive particle is 0.05-1.0 micrometer, and it is more preferable that it is 0.07-0.7 micrometer. In the present invention, the average particle diameter of the conductive particles is a value measured by a centrifugal sedimentation method.

  Furthermore, the content of the conductive particles as the filler is preferably 1.0 to 90% by mass and more preferably 5.0 to 80% by mass with respect to the total mass of the conductive layer. The conductive film may contain fluorine or antimony as necessary.

  Examples of the binder resin used for the conductive layer include phenol resin, polyurethane, polyamide, polyimide, polyamideimide, polyamic acid, polyvinyl acetal, epoxy resin, acrylic resin, melamine resin, and polyester. These resins may be used alone or in combination of two or more. When these resins are used, the adhesion of the conductive layer to the conductive support is good, the dispersibility of the conductive particles is improved, and the solvent resistance after film formation is good. preferable. Among the above resins, phenol resin, polyurethane, and polyamic acid are particularly preferable.

The conductive layer can be formed, for example, by dip coating or coating with a Meyer bar. The thickness of the conductive layer is preferably 0.1 to 30 μm, and more preferably 0.5 to 20 μm. The volume resistivity of the conductive layer is preferably 1.0 × 10 ⁵ Ω · cm or more and 1.0 × 10 ¹³ Ω · cm or less, and 1.0 × 10 ⁵ Ω · cm or more and 1.0 × More preferably, it is 10 ¹² Ω · cm or less.

  In the present invention, the volume resistivity is defined as follows: a conductive layer to be measured is formed on an aluminum plate, a gold thin film is further formed on the conductive layer, and a current value flowing between both the aluminum plate and the gold thin film is determined. , Measured using a pA meter. Furthermore, a leveling agent may be added to the conductive layer in order to improve surface properties.

  The electrophotographic photoreceptor of the present invention has a conductive support, an intermediate layer provided on the conductive support, and a photosensitive layer provided on the intermediate layer. As the photosensitive layer, a single layer type and a multilayer type are known. The laminated photosensitive layer preferably comprises at least a charge generation layer and a charge transport layer.

  The charge generation layer is preferably formed containing a charge generation material, a binder resin, and other components. The charge generation layer is obtained by, for example, dissolving a binder resin in a solvent, adding a charge generation material thereto, applying a charge generation layer coating solution obtained by dispersing the charge generation material, and drying the solution. Can be formed. In dispersing the charge generating material, a media type dispersing machine such as a sand mill or a ball mill, or a liquid collision type dispersing machine can be used.

  Examples of charge generation materials include pyrylium dyes, thiopyrylium dyes, phthalocyanine pigments, anthanthrone pigments, dibenzpyrenequinone pigments, pyratron pigments, azo pigments, indigo pigments, quinacridone pigments, and quinocyanine pigments. Dyes. Examples of the phthalocyanine pigment include metal-free phthalocyanine, halogenated gallium phthalocyanine such as oxytitanium phthalocyanine, hydroxygallium phthalocyanine, and chlorogallium phthalocyanine. These charge generation materials can be used alone or as a mixture.

  In the charge generation layer, when a charge generation material other than the phthalocyanine pigment and the phthalocyanine pigment is mixed and used, it is also preferable that the charge generation material other than the phthalocyanine pigment is contained up to 50% by mass with respect to the total charge generation material. It is. In this case, as a charge generating substance other than the phthalocyanine pigment, for example, selenium-tellurium, pyrylium, thiapyrylium dye, anthanthrone, dibenzpyrenequinone, trisazo, cyanine, disazo, monoazo, indigo, quinacridone, and asymmetric quinocyanine Pigments.

  The charge generation layer is a homogenizer, ultrasonic dispersion, ball mill, vibration ball mill, sand mill, attritor, roll mill, liquid collision type high speed disperser together with a binder resin and solvent in an amount of 0.3 to 4 times the mass ratio of the charge generation material. It can be formed by applying a coating solution for charge generation layer obtained by dispersing using a dispersing machine such as the above and drying it. Examples of the binder resin include butyral resin, polyester resin, polycarbonate resin, polyarylate resin, polystyrene resin, polyvinyl methacrylate resin, polyvinyl acrylate resin, polyvinyl acetate resin, polyvinyl chloride resin, polyamide resin, polyurethane resin, and silicone resin. Alkyd resin, epoxy resin, cellulose resin, and melamine resin, but are not limited thereto. Of these, a butyral resin is particularly preferred.

  The charge transport layer preferably contains a molecularly dispersed charge transport material and a binder resin. The charge transport layer can be formed by applying a charge transport layer coating solution obtained by dissolving a binder resin having a film-forming property and a charge transport material, and drying it. Examples of the charge transport material include polycyclic aromatic compounds, heterocyclic compounds, hydrazone compounds, styryl compounds, benzidine compounds, triarylamine compounds, triphenylamine, or groups composed of these compounds. Examples include, but are not limited to, polymers in the chain or side chain.

  Examples of the binder resin used for the charge transport layer include, but are not limited to, polyester, polycarbonate, polymethacrylic acid ester, polyarylate, polysulfone, and polystyrene. Of these, polycarbonate and polyarylate are particularly preferred.

  The process cartridge of the present invention integrally supports the electrophotographic photosensitive member of the present invention and at least one means selected from the group consisting of a charging means, a developing means, a transfer means, and a cleaning means. The process cartridge is detachable.

  The electrophotographic apparatus of the present invention is an electrophotographic apparatus having the electrophotographic photosensitive member of the present invention, a charging unit, an exposing unit, a developing unit and a transfer unit.

  FIG. 1 shows an example of a schematic configuration of an electrophotographic apparatus provided with a process cartridge having the electrophotographic photosensitive member of the present invention.

  In FIG. 1, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member, which is driven to rotate about a shaft 2 in a direction indicated by an arrow at a predetermined peripheral speed. The peripheral surface (surface) of the electrophotographic photosensitive member 1 that is driven to rotate is uniformly charged to a predetermined negative potential by a charging unit 3 (primary charging unit), and then exposed such as slit exposure or laser beam scanning exposure. Exposure light (image exposure light) 4 output from means (not shown) is received. In this way, electrostatic latent images corresponding to the target image are sequentially formed on the peripheral surface of the electrophotographic photosensitive member 1. The voltage applied to the charging unit 3 may be either a voltage obtained by superimposing an AC component on a DC component or a voltage containing only a DC component. In the present invention, a charging unit that applies only a DC component is used.

  The electrostatic latent image formed on the peripheral surface of the electrophotographic photosensitive member 1 is developed with toner of the developing means 5 to become a toner image. Next, the toner image formed and supported on the peripheral surface of the electrophotographic photosensitive member 1 is sequentially transferred by a transfer bias from the transfer unit 6 (transfer roller). The transfer material P (paper or the like) is taken out from the transfer material supply means (not shown) between the electrophotographic photoreceptor 1 and the transfer means 6 (contact portion) in synchronization with the rotation of the electrophotographic photoreceptor 1. Be fed. The transfer material P that has received the transfer of the toner image is separated from the peripheral surface of the electrophotographic photosensitive member 1 and is introduced into the fixing means 8 to receive the image fixing, and is printed out of the apparatus as an image formed product (print, copy). Be out.

  The surface of the electrophotographic photosensitive member 1 after the transfer of the toner image is cleaned by removing the developer (toner) remaining after transfer by a cleaning means 7 (cleaning blade), and further from a pre-exposure means (not shown). After being neutralized by the pre-exposure light 11, it is repeatedly used for image formation. As the transfer means, for example, an intermediate transfer type transfer means using a belt-like or drum-like intermediate transfer member may be employed. In FIG. 1, an electrophotographic photosensitive member 1, a charging unit 3, a developing unit 5 and a cleaning unit 7 are integrally supported to form a cartridge, and an electrophotography is performed using a guide unit 10 such as a rail of an electrophotographic apparatus main body. The process cartridge 9 is detachable from the apparatus main body.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. The following “parts” means “parts by mass”.

  Using a polyolefin resin containing (A1), (A2), and (A3) having the composition and mass ratio (%) shown in Table 1 below, an electrophotographic photosensitive member was produced by the method described below. In Table 1, (A1) type, (A2) type and (A3) type are shown by names of monomers before polymerization.

<Example 1>
75.0 g of resin (B-1), 60.0 g of 2-propanol (hereinafter referred to as IPA), 5.1 g of triethylamine in a hermetically sealed 1 liter glass container equipped with a heater and equipped with a heater. (Hereinafter referred to as TEA) and 159.9 g of distilled water were added and stirred at a stirring blade rotation speed of 300 rpm. No sedimentation of resin particles was observed at the bottom of the vessel, and the suspension was in a floating state. Was confirmed. Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the system temperature was kept at 140 to 145 ° C. and further stirred for 20 minutes. Then, after putting in a water bath and cooling to room temperature (about 25 ° C.) while stirring at a rotational speed of 300 rpm, pressure filtration (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) Then, an aqueous dispersion (C-1) containing milky white uniform polyolefin resin particles was obtained.

  On the other hand, 0.2 mol of stannic chloride pentahydrate was dissolved in 200 ml of water to form a 0.5 M aqueous solution, and 28% aqueous ammonia was added with stirring to add a white tin oxide superoxide of pH 1.5. A slurry containing fine particles was obtained. The obtained tin oxide ultrafine particle-containing slurry is heated to 70 ° C. and then naturally cooled to around 50 ° C., and then pure water is added to obtain a 1 liter tin oxide ultrafine particle-containing slurry, which is solid-liquid using a centrifuge. Separation was performed. After adding 800 ml of pure water to this water-containing solid content, stirring and dispersing with a homogenizer, washing was performed by solid-liquid separation using a centrifuge. 75 ml of pure water was added to the water-containing solid content after washing to prepare a tin oxide ultrafine particle-containing slurry. To the obtained tin oxide ultrafine particle-containing slurry, 3.0 ml of triethylamine was added and stirred. After the transparency was raised, the temperature was raised to 70 ° C., then the heating was stopped and the solid content was cooled to 20 mass by solid cooling. A tin oxide sol solution containing 1% of organic amine as a dispersion stabilizer was obtained. 99 parts of aqueous dispersion (C-1), 875 parts of the above tin oxide sol solution and 350 parts of IPA were mixed to prepare a coating solution for an intermediate layer.

An aluminum base tube (ED tube: JIS-A3003) having an outer diameter of 30.5 mm, an inner diameter of 28.5 mm, and a length of 260.5 mm obtained by hot extrusion was prepared as a conductive support. 120 parts of powder composed of fine particles of barium sulfate having a coating layer formed of tin oxide (coverage: 50 mass%, specific resistance of powder: 700 Ω · cm) and resol type phenol resin (trade name: Pryofen J-325, large Prepare a solution consisting of 70 parts of Nippon Ink Chemical Co., Ltd. (solid content 70%) and 100 parts of 2-methoxy-1-propanol, and disperse the powder for about 20 hours using a ball mill. A layer coating solution was prepared (the average particle size of the powder contained in this coating solution was 0.22 μm). The conductive layer coating solution was dip-coated on a conductive support and heated and cured at 140 ° C. for 30 minutes to form a conductive layer having a thickness of 15 μm.
The intermediate layer coating solution was dip-coated on this conductive layer and dried at 120 ° C. for 10 minutes to form an intermediate layer having a thickness of 0.8 μm.

  Next, 10 parts of polyvinyl butyral resin (trade name: BX-1, manufactured by Sekisui Chemical Co., Ltd.) and 350 parts of cyclohexanone are added to 20 parts of hydroxygallium phthalocyanine crystal as a charge generating substance, and glass beads having a diameter of 1 mm are used. The mixture was dispersed in a sand mill for 3 hours, and 1200 parts of ethyl acetate was added thereto for dilution to prepare a charge generation layer coating solution. At this time, the dispersed particle size of the charge generating material in the coating solution measured using a natural / centrifugal sedimentation particle size distribution measuring apparatus (CAPA-700, manufactured by Horiba, Ltd.) was 0.15 μm. On the intermediate layer, this charge generation layer coating solution was applied by dip coating and dried at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.2 μm.

  Next, 7 parts of a compound represented by the following structural formula (7), 1 part of a compound represented by the following structural formula (8), and a bisphenol C-type polyarylate resin having a structural unit represented by the following structural formula (9) A charge transport layer coating solution was prepared by dissolving 10 parts (weight average molecular weight [Mw] 110,000) in a mixed solvent consisting of 50 parts of monochlorobenzene and 10 parts of dichloromethane. This charge transport layer coating solution was dip-coated on the charge generation layer and dried at 110 ° C. for 1 hour to form a charge transport layer having a thickness of 18 μm. Thus, an electrophotographic photosensitive member was produced.

The evaluation method of the electrophotographic photosensitive member is as follows.
The electrophotographic photosensitive member produced above was converted into a color laser printer manufactured by Hewlett-Packard Co., Ltd., a modified laser jet 4600 (charging: roller contact DC charging, dark part potential -500 V, process speed 100 mm / second, laser exposure, light intensity 0 3 μJ / cm ² ), the light potential at 23 ° C./50% RH at normal temperature and humidity was measured, and this was taken as the sensitivity of the electrophotographic photosensitive member. Further, after measuring the bright portion potential at a low temperature and low humidity of 15 ° C./10% RH, 3000 images were output at an image density of 4%, and the bright portion potential was measured again. The difference in bright part potential between the normal temperature and normal humidity environment and the low temperature and low humidity environment was defined as the environmental fluctuation value, and the bright part potential difference before and after the image output was defined as the durable potential fluctuation value. The results are shown in Table 2. The sensitivity is preferably less than 130 V, and the environmental fluctuation value and the endurance potential fluctuation value are preferably 20 V or less and 19 V or less, respectively. When the environmental fluctuation and the endurance potential fluctuation value are large, the obtained image density change is also large, more preferably 15 V or less and 18 V or less, respectively, and when image density stability is required, 10 V or less and 15 V or less, respectively. It is.

<Example 2>
To 100 parts of titanium oxide (TTO55N, manufactured by Ishihara Sangyo Co., Ltd.), 750 parts of methanol and 50 parts of distilled water, 1,000 parts of 1 mm diameter glass beads are added and dispersed for 15 hours using a paint shaker. Obtained. An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the tin oxide sol solution of the intermediate layer coating solution in Example 1 was changed to 900 parts of the titanium oxide dispersion. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 2.

<Example 3>
An electrophotographic photosensitive member was produced in the same manner as in Example 2 except that titanium oxide was changed to (titanium oxide, PT401M, manufactured by Ishihara Sangyo Co., Ltd.). The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 2.

<Example 4>
An electrophotographic photosensitive member was produced in the same manner as in Example 2 except that titanium oxide was changed to titanium oxide (PT301M, manufactured by Ishihara Sangyo Co., Ltd.). The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 2.

<Example 5>
25 parts of the compound represented by the following structural formula (10) was dissolved in a mixed solvent of 350 parts of cyclohexanone and 350 parts of methanol. An electrophotographic photoreceptor was prepared in the same manner as in Example 1 except that the tin oxide sol solution of the intermediate layer coating solution was changed to 725 parts of the compound solution represented by the structural formula (10). The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 2.

The compound represented by the structural formula (10) can be synthesized using a known synthesis method described in US Pat. No. 4,442,193, US Pat. No. 4,992,349, and US Pat. No. 5,468,583. . Specifically, it was synthesized by the following method. Under a nitrogen stream, 1,4,5,8-naphthalenetetracarboxylic dianhydride (20 parts) and imidazole (1 part) were mixed, and 2-methyl-6-ethylaniline (50 parts) and 2-amino-1-butanol (7.3) were mixed. Part was added and heated and stirred at 170 ° C. for 3 hours. After completion of the reaction, 500 ml of toluene was added and separation and purification were performed by silica gel column chromatography. The resulting brown liquid was heated and then cooled to obtain 10 parts of yellowish white crystals. When the molecular weight was measured by mass spectrometry using MALDI-TOF MS (ultraflex manufactured by Bruker Daltonics, Inc., acceleration voltage: 20 kV, mode: Reflector, molecular weight standard product: fullerene C ₆₀ ), 456 was obtained as the peak top value. It was. Moreover, it confirmed that it was a compound shown by Structural formula (10) from an infrared absorption spectrum and proton NMR.

The infrared absorption spectrum was measured using a Fourier transform infrared spectrophotometer (trade name: Paragon 1000) manufactured by PerkinElmer Japan, with a KBr tablet method with a resolution of 4 cm ⁻¹ , and NMR using R-1100 manufactured by Hitachi, Ltd. Solvent: CDCl3, concentration 10%, internal standard TMS.

<Example 6>
An electrophotographic photoreceptor was prepared in the same manner as in Example 5 except that the compound represented by the structural formula (10) in Example 5 was changed to the compound represented by the following structural formula (11). The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 2.

構造式（１１）で示される化合物は、構造式（１０）で示される化合物の合成で用いた２−メチル−６−エチルアニリンおよび２−アミノ−１−ブタノールを２−６−ジエチル−３クロロアニリンおよび２−メチル−４ニトロアニリンに変更した以外は同様に合成した。

The compound represented by the structural formula (11) is obtained by replacing 2-methyl-6-ethylaniline and 2-amino-1-butanol used in the synthesis of the compound represented by the structural formula (10) with 2-6-diethyl-3chloro. The synthesis was performed in the same manner except that the aniline and 2-methyl-4nitroaniline were changed.

<Example 7>
In Example 5, an electrophotographic photosensitive member was produced in the same manner as in Example 5 except that the compound represented by the structural formula (10) was changed to the compound represented by the following structural formula (12). The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 2.

構造式（１２）で示される化合物は、構造式（１０）で示される化合物の合成で用いた２−メチル−６−エチルアニリンを２−６−ジエチル−３クロロアニリンに変更した以外は同様に合成した。

The compound represented by Structural Formula (12) is the same except that 2-methyl-6-ethylaniline used in the synthesis of the compound represented by Structural Formula (10) was changed to 2-6-diethyl-3chloroaniline. Synthesized.

<Example 8>
An aqueous dispersion (C-13) containing polyolefin resin particles was prepared in the same manner as in Example 1 except that the resin (B-1) was changed to the resin (B-13) shown in Table 1 in Example 1. did. Then, an electrophotographic photosensitive member was produced in the same manner as in Example 1 except that 99 parts of an aqueous dispersion (C-13), 700 parts of distilled water and 200 parts of IPA were mixed to prepare an intermediate layer coating solution. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 2.

<Example 9>
In Example 1, except that 80 parts of aqueous dispersion (C-1), 875 parts of tin oxide sol solution, 5 parts of N-methoxymethylated nylon 6 and 350 parts of IPA were mixed to prepare an intermediate layer coating solution. An electrophotographic photosensitive member was produced in the same manner as in Example 1. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 2.

<Example 10>
An aqueous dispersion (C-14) containing polyolefin resin particles was prepared in the same manner as in Example 1 except that the resin (B-1) was changed to the resin (B-14) shown in Table 1 in Example 1. did. Then, 99 parts of an aqueous dispersion (C-14), 700 parts of distilled water and 200 parts of IPA were mixed to prepare an intermediate layer coating solution, and the film thickness of the intermediate layer was changed to 0.3 μm. Similarly, an electrophotographic photosensitive member was produced. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Example 11>
In Example 1, the resin (B-1) was changed to the resin (B-2) to prepare an aqueous dispersion (C-2). Then, 99 parts of aqueous dispersion (C-2), 835 parts of distilled water and 65 parts of IPA were mixed to prepare an intermediate layer coating solution, and the film thickness of the intermediate layer was set to 0.3 μm. Similarly, an electrophotographic photosensitive member was produced. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Example 12>
In Example 1, 99 parts of the aqueous dispersion (C-1), 645 parts of distilled water and 280 parts of IPA were mixed to prepare an intermediate layer coating solution, and this was performed except that the film thickness of the intermediate layer was 0.3 μm. An electrophotographic photosensitive member was produced in the same manner as in Example 1. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Example 13>
The resin (B-14) used in Example 10 was changed to the resin (B-3) shown in Table 1 to obtain an aqueous dispersion (C-3) containing resin particles, as in Example 10. An electrophotographic photosensitive member was produced. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Example 14>
60 parts of aqueous dispersion (C-1), 700 parts of distilled water, 200 parts of IPA, and 10 parts of N-methoxymethylated 6 nylon were mixed to prepare a coating solution for the intermediate layer. The thickness of the intermediate layer was 0.3 μm. An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Example 15>
The resin (B-14) used in Example 10 was changed to the resin (B-4) shown in Table 1, and the resin particle-containing aqueous dispersion (C-4) was used. An electrophotographic photosensitive member was produced. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Example 16>
The resin (B-14) used in Example 10 was changed to the resin (B-5) shown in Table 1 to obtain an aqueous dispersion (C-5) containing resin particles, as in Example 10. An electrophotographic photosensitive member was produced. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Example 17>
The resin (B-14) used in Example 10 was changed to the resin (B-6) shown in Table 1 to obtain an aqueous dispersion (C-6) containing resin particles, and was the same as in Example 10. An electrophotographic photosensitive member was produced. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Example 18>
The resin (B-14) used in Example 10 was changed to the resin (B-7) shown in Table 1 to obtain an aqueous dispersion (C-7) containing resin particles, as in Example 10. An electrophotographic photosensitive member was produced. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Example 19>
The resin (B-14) used in Example 10 was changed to the resin (B-8) shown in Table 1 to obtain an aqueous dispersion (C-8) containing resin particles, as in Example 10. An electrophotographic photosensitive member was produced. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Example 20>
The resin (B-14) used in Example 10 was changed to the resin (B-9) shown in Table 1 to obtain an aqueous dispersion (C-9) containing resin particles, as in Example 10. An electrophotographic photosensitive member was produced. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Example 21>
The resin (B-14) used in Example 10 was changed to the resin (B-10) shown in Table 1, and the resin particle-containing aqueous dispersion (C-10) was used. An electrophotographic photosensitive member was produced. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Example 22>
The resin (B-14) used in Example 10 was changed to the resin (B-11) shown in Table 1 to obtain an aqueous dispersion containing resin particles (C-11). An electrophotographic photosensitive member was produced. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Comparative Example 1>
The resin (B-14) used in Example 10 was changed to the resin (B-12) shown in Table 1 to obtain an aqueous dispersion containing resin particles (C-12). An electrophotographic photosensitive member was produced. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Comparative example 2>
The resin (B-14) used in Example 10 was changed to the resin (B-15) shown in Table 1 to obtain an aqueous dispersion (C-15) containing resin particles, as in Example 10. An electrophotographic photosensitive member was produced. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Comparative Example 3>
The resin (B-14) used in Example 10 was changed to the resin (B-16) shown in Table 1 to obtain an aqueous dispersion containing resin particles (C-16). An electrophotographic photosensitive member was produced. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Comparative example 4>
The resin (B-14) used in Example 10 was changed to the resin (B-17) shown in Table 1 to obtain an aqueous dispersion containing resin particles (C-17). An electrophotographic photosensitive member was produced. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Comparative Example 5>
An electrophotographic photosensitive member was produced in the same manner as in Example 10 except that SG2000 (produced by Lead City Corporation), which is an aqueous solution of ethylene and an acrylic acid copolymer resin, was used as the coating solution for the intermediate layer. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Comparative Example 6>
An electrophotographic photosensitive member was prepared in the same manner as in Example 10, except that 10 parts of ELVAX 4260 (manufactured by DuPont), which is a copolymer resin of ethylene and vinyl acetate, was dissolved in 200 parts of toluene as the coating solution for the intermediate layer. did. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Comparative Example 7>
An electrophotographic photosensitive member was produced in the same manner as in Example 10 except that 10 parts of super cron (manufactured by Nippon Paper Industries Co., Ltd.) and 200 parts of toluene were used as the intermediate layer coating solution. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are shown in Table 3.

1 Electrophotographic photoreceptor 2 Axis 3 Charging means (primary charging means)
4 exposure light (image exposure light)
5 Developing means 6 Transfer means (transfer roller)
7 Cleaning means (cleaning blade)
8 Fixing means 9 Process cartridge 10 Guide means 11 Pre-exposure light P Transfer material (paper, etc.)

Claims (6)

In an electrophotographic photoreceptor having a conductive support, an intermediate layer provided on the conductive support, and a photosensitive layer provided on the intermediate layer,
The intermediate layer contains a polyolefin resin having the following (A1), (A2) and (A3), and the mass ratio (%) of (A2) in the polyolefin resin is 0.01% by mass or more and 30% by mass or less. An electrophotographic photoreceptor, characterized in that
(A1): Repeating structural unit represented by the following formula (11)

(In formula (11), R ^{11 to} R ¹⁴ each independently represents a hydrogen atom or an alkyl group.) (A2): Repeating structural unit represented by the following formula (21) or (22)

(In the formulas (21) and (22), R ^{21 to} R ²⁴ each independently represents a hydrogen atom, an alkyl group, a phenyl group or —Y ²¹ COOH (Y ²¹ represents a single bond, an alkylene group or an arylene group). .), R ²⁵ and R ²⁶ each independently represent a hydrogen atom, an alkyl group or a phenyl group, and X ²¹ represents —Y ²² COOCOY ²³ — (Y ²² and Y ^23. Each independently represents a single bond, an alkylene group or an arylene group.), Wherein at least one of R ^{21 to} R ²⁴ is a monovalent group represented by —Y ²¹ COOH. The base of
(A3): repeating structural unit represented by the following formula (31), (32), (33) or (34)

(In formulas (31) to (34), R ^{31 to} R ³⁵ each independently represent a hydrogen atom or a methyl group, and R ^{41 to} R ⁴³ each independently represents an alkyl group having 1 to 10 carbon atoms. R ^{51 to} R ⁵³ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.) The electrophotographic photosensitive member according to claim 1, wherein the polyolefin resin satisfies the following formulas (I) and (II) in a mass ratio (%) of (A1), (A2), and (A3).
Formula (I): 0.01 ≦ (A2) / {(A1) + (A2) + (A3)} × 100 ≦ 10
Formula (II): 55/45 ≦ (A1) / (A3) ≦ 99/1 The electrophotographic photosensitive member according to claim 2, wherein the polyolefin resin satisfies the following formula (III) in a mass ratio (%) of (A1), (A2), and (A3).
Formula (III): 0.01 ≦ (A2) / {(A1) + (A2) + (A3)} × 100 ≦ 5   The polyolefin resin is an ethylene-maleic anhydride-acrylic acid ester terpolymer or an ethylene-maleic anhydride-methacrylic acid ester terpolymer. 2. The electrophotographic photosensitive member according to item 1.   An electrophotographic photosensitive member according to any one of claims 1 to 4 and at least one means selected from the group consisting of a charging means, a developing means, a transfer means and a cleaning means are integrally supported, and an electrophotographic A process cartridge that is detachable from the main unit.   An electrophotographic apparatus comprising the electrophotographic photosensitive member according to claim 1, a charging unit, an exposure unit, a developing unit, and a transfer unit.

Images